Tailoring MoS2 Valley‐Polarized Photoluminescence with Super Chiral Near‐Field

Transition metal dichalcogenides with intrinsic spin–valley degrees of freedom hold great potentials for applications in spintronic and valleytronic devices. MoS₂ monolayer possesses two inequivalent valleys in the Brillouin zone, with each valley coupling selectively with circularly polarized photons. The degree of valley polarization (DVP) is a parameter to characterize the purity of valley‐polarized photoluminescence (PL) of MoS₂ monolayer. Usually, the detected values of DVP in MoS₂ monolayer show achiral property under optical excitation of opposite helicities due to reciprocal phonon‐assisted intervalley scattering process. Here, it is reported that valley‐polarized PL of MoS₂ can be tailored through near‐field interaction with plasmonic chiral metasurface. The resonant field of the chiral metasurface couples with valley‐polarized excitons, and tailors the measured PL spectra in the far‐field, resulting in observation of chiral DVP of MoS₂‐metasurface under opposite helicities excitations. Valley‐contrast PL in the chiral heterostructure is also observed when illuminated by linearly polarized light. The manipulation of valley‐polarized PL in 2D materials using chiral metasurface represents a viable route toward valley‐polaritonic devices.     

Locking and Unlocking the Molecular Spin Crossover Transition

The Fe(II) spin crossover complex [Fe{H₂B(pz)₂}₂(bipy)] (pz = pyrazol‐1‐yl, bipy = 2,2′‐bipyridine) can be locked in a largely low‐spin‐state configuration over a temperature range that includes temperatures well above the thermal spin crossover temperature of 160 K. This locking of the spin state is achieved for nanometer thin films of this complex in two distinct ways: through substrate interactions with dielectric substrates such as SiO₂ and Al₂O₃, or in powder samples by mixing with the strongly dipolar zwitterionic p ‐benzoquinonemonoimine C₆H₂(—? NH₂)₂(—? O)₂. Remarkably, it is found in both cases that incident X‐ray fluences then restore the [Fe{H₂B(pz)₂}₂(bipy)] moiety to an electronic state characteristic of the high spin state at temperatures of 200 K to above room temperature; that is, well above the spin crossover transition temperature for the pristine powder, and well above the temperatures characteristic of light‐ or X‐ray‐induced excited‐spin‐state trapping. Heating slightly above room temperature allows the initial locked state to be restored. These findings, supported by theory, show how the spin crossover transition can be manipulated reversibly around room temperature by appropriate design of the electrostatic and chemical environment.     

Magneto‐Photoluminescence Based on Two‐Photon Excitation in Lanthanide‐Doped Up‐Conversion Crystal Particles

Experimental studies on magneto‐photoluminescence based on two‐photon excitation in up‐conversion Y₂O₂S:Er, Yb crystal particles are reported. It is found that the up‐conversion photoluminescence generated by two‐photon excitation exhibits magnetic field effects at room temperature, leading to a two‐photon excitation‐induced magneto‐photoluminescence, when the two‐photon excitation exceeds the critical intensity. By considering the spin selection rule in electronic transitions, it is proposed that spin‐antiparallel and spin‐parallel transition dipoles with spin mixing are accountable for the observed magneto‐photoluminescence. Specifically, the two‐photon excitation generates spin‐antiparallel electric dipoles between ⁴S_3/2–⁴I_15/2 in Er³⁺ ions. The antiparallel spins are conserved by exchange interaction within dipoles. When the photoexcitation exceeds the critical intensity, the Coulomb screening can decrease the exchange interaction. Consequently, the spin–orbital coupling can partially convert the antiparallel dipoles into parallel dipoles, generating a spin mixing. Eventually, the populations between antiparallel and parallel dipoles reach an equilibrium established by the competition between exchange interaction and spin–orbital coupling. Applying a magnetic field can break the equilibrium by disturbing spin mixing through introducing spin precessions, changing the spin populations on antiparallel and parallel dipoles and leading to the magneto‐photoluminescence. Therefore, spin‐dependent transition dipoles present a convenient mechanism to realize magneto‐photoluminescence in multiphoton up‐conversion crystal particles.     

Spin Diffusion Anisotropy in Liquid 3He

We report new experiments on the transverse and longitudinal spin dynamics of liquid ³ He polarized by an 11.3T field. At the lowest temperatures probed, the transverse spin diffusion coefficient saturates with an apparent anisotropy temperature of T_a=12±2 mK. This temperature dependence is in accord with the general idea of spin-diffusion anisotropy but the value of T_a is half that expected from extrapolating earlier experiments at a lower field. Strong magnetostatic effects in the form of long-lived spin modes are also observed for small gradients and small tipping angles.     

Energy‐Tailorable Spin‐Selective Multifunctional Metasurfaces with Full Fourier Components

Compact integrated multifunctional metasurface that can deal with concurrent tasks represent one of the most profound research fields in modern optics. Such integration is expected to have a striking impact on minimized optical systems in applications such as optical communication and computation. However, arbitrary multifunctional spin‐selective design with precise energy configuration in each channel is still a challenge, and suffers from intrinsic noise and complex designs. Here, a design principle is proposed to realize energy tailorable multifunctional metasurfaces, in which the functionalities can be arbitrarily designed if the channels have no or weak interference in k‐space. A design strategy is demostrated here with high‐efficiency dielectric nanopillars that can modulate full Fourier components of the optical field. The spin‐selective behavior of the dielectric metasurfaces is also investigated, which originates from the group effect introduced by numerous nanopillar arrays. This approach provides straightforward rules to control the functionality channels in the integrated metasurfaces, and paves the way for efficient concurrent optical communication.     

Multiaxial fatigue of V‐notched steel specimens: a non‐conventional application of the local energy method

The paper deals with the multi‐axial fatigue strength of notched specimens made of 39NiCrMo3 hardened and tempered steel. Circumferentially V‐notched specimens were subjected to combined tension and torsion loading, both in‐phase and out‐of‐phase, under two nominal load ratios, R=?1 and R= 0, also taking into account the influence of the biaxiality ratio, λ=τ_a/σ_a. The notch geometry of all axi‐symmetric specimens was a notch tip radius of 0.1 mm, a notch depth of 4 mm, an included V‐notch angle of 90° and a net section diameter of 12 mm. The results from multi‐axial tests are discussed together with those obtained under pure tension and pure torsion loading on plain and notched specimens. Furthermore the fracture surfaces are examined and the size of non‐propagating cracks measured from some run‐out specimens at 5 million cycles. Finally, all results are presented in terms of the local strain energy density averaged in a given control volume close to the V‐notch tip. The control volume is found to be dependent on the loading mode.     

Engineering High‐Performance MoO2‐Based Nanomaterials with Supercapacity and Superhydrophobicity by Tuning the Raw Materials Source

Herein, a simple self‐assembly method is proposed for the fabrication of MoO₂‐based superhydrophobic material with record high contact angles (contact angle up to about 173°) for conductive metal oxides on hard/soft substrates. The spin‐coated surface demonstrates excellent oil–water separation efficiency (>98%) after 50 cycles and robust corrosion resistance after immersion into different pH solutions for 20 d. These water‐resistant coatings retain excellent superhydrophobicity after oil immersion, knife‐scratch, and long‐cycle sandpaper abrasion, which is not observed on most artificial surfaces. Meanwhile, the functionality switching from superhydrophobicity to supercapacity, which have an inverse relationship in aqueous solutions because of poor electrode wettability, is achieved simply by editing the raw materials source. Tuning of the raw materials leads to the same product MoO₂/graphitic carbon with different morphologies and functionalities. Different from superhydrophobic MoO₂/carbon ball flowers, MoO₂ nanotubes with carbon exhibit excellent supercapacity with a large gravimetric capacitance and great cycling stability.     

Stability of Surface‐Enhanced Ultrahydrophilic Metals as a Basis for Bioactive rhBMP‐2 Surfaces

For several years the treatment of metals like cp titanium and 316L stainless steel with concentrated chromosulfuric acid at high temperatures (230‐240 °C) has formed the basis for preparing ultra‐hydrophilic priming coats on these metals (Jennissen et al. Materialwiss. Werkstofftech. 30, 838‐845, 1999). Metals treated in this way have been called surface‐enhanced, displaying a characteristic ultrastructure, and can be easily modified to carry a biocoat of recombinant human bone morphogenetic protein 2 (rhBMP‐2). The major oxide on surface enhanced titanium is TiO₂. Thus this TiO₂‐layer could be responsible for the ultra‐hydrophilic properties of the priming coat. Irradiation of TiO₂ layers by ultraviolet light (Wang et al., Nature 388, 431‐432, 1997) has been shown to endow these layers with ultra‐hydrophilic properties (i.e. contact angles of ～ 0°). However the ultra‐hydrophilic TiO₂‐layers produced by irradiation are unstable and revert to the original high contact angles of ～ 70° within several days. The question of whether the ultra‐hydrophilic surfaces prepared by the chromosulfuric acid method show long‐term stability was therefore important to answer. In addition the question if rhBMP‐2 immobilized on such a surface will retain its biological activity was of great interest. In this paper it will be shown that ultrahydrophilic titanium mini‐plates retain their ultra‐hydrophilicity with contact angles of 0‐8° unchanged for at least 50 days and support the immobilization of rhBMP‐2 in a biologically active form.     

An integrated solution for NOx‐reduction and ‐control under lean‐burn conditions

Upcoming emission regulations order highly effective NO_x‐reduction systems in lean‐burn engines requiring new catalytic materials and integrated control of the reduction process. Thus, new approaches for NO_x‐reduction and its monitoring over an On‐Board‐Diagnostic (OBD) system are suggested throughout the globe. A promising attempt is the development of a catalytic system having an integrated NO_x‐sensor, based on selective catalytic reduction process and impedance sensors. The study displays the results achieved both with a perovskite type of self‐regenerative catalyst functioning by H₂‐reductant and with impedance NO_x‐sensors. The catalysts were tested at the temperature range of 150 °C to 360 °C yielding NO_x conversion rates of 92 % with high selectivity to N₂. Impedance sensors having NiCr₂O₄‐ and NiO‐SE and PYSZ‐ and FYSZ‐electrolytes are developed and tested at 600 °C under lean atmosphere (5 vol. % O₂). Better sensing behaviour towards NO and lower cross‐selectivity towards O₂, CO, CO₂ and CH₄ have been observed with sensors having NiO‐SE.     

Organic Spin‐Valves and Beyond: Spin Injection and Transport in Organic Semiconductors and the Effect of Interfacial Engineering

Since the first observation of the spin‐valve effect through organic semiconductors, efforts to realize novel spintronic technologies based on organic semiconductors have been rapidly growing. However, a complete understanding of spin‐polarized carrier injection and transport in organic semiconductors is still lacking and under debate. For example, there is still no clear understanding of major spin‐flip mechanisms in organic semiconductors and the role of hybrid metal–organic interfaces in spin injection. Recent findings suggest that organic single crystals can provide spin‐transport media with much less structural disorder relative to organic thin films, thus reducing momentum scattering. Additionally, modification of the band energetics, morphology, and even spin magnetic moment at the metal–organic interface by interface engineering can greatly impact the efficiency of spin‐polarized carrier injection. Here, progress on efficient spin‐polarized carrier injection into organic semiconductors from ferromagnetic metals by using various interface engineering techniques is presented, such as inserting a metallic interlayer, a molecular self‐assembled monolayer (SAM), and a ballistic carrier emitter. In addition, efforts to realize long spin transport in single‐crystalline organic semiconductors are discussed. The focus here is on understanding and maximizing spin‐polarized carrier injection and transport in organic semiconductors and insight is provided for the realization of emerging organic spintronics technologies.     

Probing the Domain Architecture in 2D α‐Mo2C via Polarized Raman Spectroscopy

MXenes are emerging 2D materials with intriguing properties such as excellent stability and high conductivity. Here, a systematic study on the Raman spectra of 2D α‐Mo₂C (molybdenum carbide), a promising member in MXene family, is conducted. Six experimentally observed Raman modes from ultrathin α‐Mo₂C crystal are first assigned with the assistance of phonon dispersion calculated from density functional theory. Angle‐resolved polarized Raman spectroscopy indicates the anisotropy of α‐Mo₂C in the b–c plane. Raman spectroscopy is further used to study the unique domain structures of 2D α‐Mo₂C crystals grown by chemical vapor deposition. A Raman mapping investigation suggests that most of the α‐Mo₂C flakes contain multiple domains and the c‐axes of neighboring domains tend to form a 60° or 120° angle, due to the weak Mo? C bonds in this interstitial carbide and the low formation energy of the carbon chains along three equivalent directions. This study demonstrates that polarized Raman spectroscopy is a powerful and effective way to characterize the domain structures in α‐Mo₂C, which will facilitate the further exploration of the domain‐structure‐related properties and potential applications of α‐Mo₂C.     

Chiral Octahydro‐Binaphthol Compound‐Based Thermally Activated Delayed Fluorescence Materials for Circularly Polarized Electroluminescence with Superior EQE of 32.6% and Extremely Low Efficiency Roll‐Off

Circularly polarized organic light‐emitting diodes (CP‐OLEDs) are particularly favorable for the direct generation of CP light, and they demonstrate a promising application in 3D display. However, up to now, such CP devices have suffered from low brightness, insufficient efficiency, and serious efficiency roll‐off. In this study, a pair of octahydro‐binaphthol ( OBN )‐based chiral emitting enantiomers, (R/S)‐OBN‐Cz , are developed by ingeniously merging a chiral source and a luminophore skeleton. These chirality–acceptor–donor (C–A–D)‐type and rod‐like compounds concurrently generate thermally activated delayed fluorescence with a small ΔE_ST of 0.037 eV, as well as a high photoluminescence quantum yield of 92% and intense circularly polarized photoluminescence with dissymmetry factors (|g_PL|) of ≈2.0 × 10^?3 in thin films. The CP‐OLEDs based on (R/S)‐OBN‐Cz enantiomers not only display obvious circularly polarized electroluminescence signals with a |g_EL| of ≈2.0 × 10^?3, but also exhibit superior efficiencies with maximum external quantum efficiency (EQE_max) up to 32.6% and extremely low efficiency roll‐off with an EQE of 30.6% at 5000 cd m^?2, which are the best performances among the reported CP devices to date.     

Tunable Modal Birefringence in a Low‐Loss Van Der Waals Waveguide

van der Waals (vdW) crystals are promising candidates for integrated phase retardation applications due to their large optical birefringence. Among the two major types of vdW materials, the hyperbolic vdW crystals are inherently inadequate for optical retardation applications since the supported polaritonic modes are exclusively transverse‐magnetic (TM) polarized and relatively lossy. Elliptic vdW crystals, on the other hand, represent a superior choice. For example, molybdenum disulfide (MoS₂) is a natural uniaxial vdW crystal with extreme elliptic anisotropy in the frequency range of optical communication. Both transverse‐electric (TE) polarized ordinary and TM polarized extraordinary waveguide modes can be supported in MoS₂ microcrystals with suitable thicknesses. In this work, low‐loss transmission of these guided modes is demonstrated with nano‐optical imaging at the near‐infrared (NIR) wavelength (1530 nm). More importantly, by combining theoretical calculations and NIR nanoimaging, the modal birefringence between the orthogonally polarized TE and TM modes is shown to be tunable in both sign and magnitude via varying the thickness of the MoS₂ microcrystal. This tunability represents a unique new opportunity to control the polarization behavior of photons with vdW materials.     

Antiferromagnetic Inverse Spinel Oxide LiCoVO4 with Spin-Polarized Channels for Water Oxidation

Exploring highly efficient catalysts for the oxygen evolution reaction (OER) is essential for water electrolysis. Cost-effective transition-metal oxides with reasonable activity are raising attention. Recently, OER reactants' and products' differing spin configurations have been thought to cause slow reaction kinetics. Catalysts with magnetically polarized channels could selectively remove electrons with opposite magnetic moment and conserve overall spin during OER, enhancing triplet state oxygen molecule evolution. Herein, antiferromagnetic inverse spinel oxide LiCoVO₄ is found to contain d⁷ Co²⁺ ions that can be stabilized under active octahedral sites, possessing high spin states S = 3/2 (t_2g⁵e_g²). With high spin configuration, each Co²⁺ ion has an ideal magnetic moment of 3 µ_B, allowing the edge-shared Co²⁺ octahedra in spinel to be magnetically polarized. Density functional theory simulation results show that the layered antiferromagnetic LiCoVO₄ studied contains magnetically polarized channels. The average magnetic moment (µ_ave) per transition-metal atom in the spin conduction channel is around 2.66 µ_B. Such channels are able to enhance the selective removal of spin-oriented electrons from the reactants during the OER, which facilitates the accumulation of appropriate magnetic moments for triplet oxygen molecule evolution. In addition, the LiCoVO₄ reported has been identified as an oxide catalyst with excellent OER activity.     

High‐Temperature Shape Memory Effect in Ti‐Ta Thin Films Sputter Deposited at Room Temperature

Ti‐Ta based alloys are potential high‐temperature shape memory materials with operation temperatures above 100 °C. In this study, the room temperature fabrication of Ti‐Ta thin films showing a reversible martensitic transformation and a high temperature shape memory effect above 200 °C is reported. In contrast to other shape memory thin films, no further heat treatment is necessary to obtain the functional properties. A disordered α″ martensite (orthorhombic) phase is formed in the as‐deposited co‐sputtered Ti₇₀Ta₃₀, Ti₆₈Ta₃₂ and Ti₆₇Ta₃₃ films, independent of the substrate. A Ti₇₀Ta₃₀ free‐standing film shows a reversible martensitic transformation, as confirmed by temperature–dependent XRD measurements during thermal cycling between 125 °C to 275 °C. Furthermore, a one‐way shape memory effect is qualitatively confirmed in this film. The observed properties of the Ti‐Ta thin films make them promising for applications on polymer substrates and especially in microsystem technologies.     

Microwave Energy Drives “On–Off–On” Spin‐Switch Behavior in Nitrogen‐Doped Graphene

The established application of graphene in organic/inorganic spin‐valve spintronic assemblies is as a spin‐transport channel for spin‐polarized electrons injected from ferromagnetic substrates. To generate and control spin injection without such substrates, the graphene backbone must be imprinted with spin‐polarized states and itinerant‐like spins. Computations suggest that such states should emerge in graphene derivatives incorporating pyridinic nitrogen. The synthesis and electronic properties of nitrogen‐doped graphene (N content: 9.8%), featuring both localized spin centers and spin‐containing sites with itinerant electron properties, are reported. This material exhibits spin‐switch behavior (on–off–on) controlled by microwave irradiation at X‐band frequency. This phenomenon may enable the creation of novel types of switches, filters, and spintronic devices using sp²‐only 2D systems.     

Highly‐Anisotropic Dion–Jacobson Hybrid Perovskite by Tailoring Diamine into CsPbBr3 for Polarization‐Sensitive Photodetection

2D materials with inherent attributes of structural anisotropy have been well applied in the field of polarization‐sensitive photodetection. However, to explore new 2D members with strong polarized‐light responses still remains a challenge. Herein, by alloying diamine molecule into the 3D prototype of CsPbBr₃, a new Dion–Jacobson (DJ) type 2D perovskite of (HDA)CsPb₂Br₇ ( 1 , where HDA²⁺ is 1,6‐hexamethylenediammonium), containing both inorganic Cs metal and organic cations is designed. The natural anisotropy characteristics of 1 are solidly elucidated by analyzing crystal structure, electric conductivity, and optical properties. Strikingly, distinct polarization‐sensitive responses are observed in 1 , owing to its strong anisotropy of optical absorption (the ratio of α_c/α_b ≈ 2.2). Consequently, crystal‐based detectors of 1 exhibit fascinating photo‐activities to polarized‐light, including high detectivity (1.5 × 10⁹ Jones), large dichroism ratio (I_ph^c/I_ph^b ≈ 1.6) and fast responding rate (200 µs). All these polarization‐sensitive performances along with intriguing phase stability make 1 a potential candidate for polarized‐light detection. This work paves a pathway toward new functionalities of DJ‐type 2D hybrid perovskites for their future optoelectronic device applications.     

MoS2 Negative‐Capacitance Field‐Effect Transistors with Subthreshold Swing below the Physics Limit

The Boltzmann distribution of electrons induced fundamental barrier prevents subthreshold swing (SS) from less than 60 mV dec^‐1 at room temperature, leading to high energy consumption of MOSFETs. Herein, it is demonstrated that an aggressive introduction of the negative capacitance (NC) effect of ferroelectrics can decisively break the fundamental limit governed by the “Boltzmann tyranny”. Such MoS₂ negative‐capacitance field‐effect transistors (NC‐FETs) with self‐aligned top‐gated geometry demonstrated here pull down the SS value to 42.5 mV dec^‐1, and simultaneously achieve superior performance of a transconductance of 45.5 μS μm and an on/off ratio of 4 × 10⁶ with channel length less than 100 nm. Furthermore, the inserted HfO₂ layer not only realizes a stable NC gate stack structure, but also prevents the ferroelectric P(VDF‐TrFE) from fatigue with robust stability. Notably, the fabricated MoS₂ NC‐FETs are distinctly different from traditional MOSFETs. The on‐state current increases as the temperature decreases even down to 20 K, and the SS values exhibit nonlinear dependence with temperature due to the implementation of the ferroelectric gate stack. The NC‐FETs enable fundamental applications through overcoming the Boltzmann limit in nanoelectronics and open up an avenue to low‐power transistors needed for many exciting long‐endurance portable consumer products.     

Technical note – the significance of chuck wall angles in the quantification of seam thickness in canned food

One of the key dimensional measures in quality control of canned foods is the double seam thickness (mm). Electronic micrometers quantify the seam thickness, based on a chuck wall angle of 4.0° due to the seaming chuck being fixed at the same angle during seaming. Investigations of chuck wall angles (n = 144) in non‐round cans by a coordinate measuring machine revealed that 93% of the chuck wall angles following seaming were off the interval 4.0 ± 0.25° (range: 3.146–10.281°, CV = 23%), indicating that the seaming process introduces a significant variance in the chuck wall angle. The aberration in the actual chuck wall angle from 4.0° introduces a bias (?) in the measured seam‐thickness (T_ms), which may cause rejection of closed cans as having unacceptable seam thickness based on incorrect measurements. The mathematical deduction of the bias introduced in the measured seam thickness when the actual chuck wall angle is aberrant from 4.0° is presented, and it is concluded that it is erroneous to neglect the chuck wall angle of sealed cans in the methodology of seam thickness determination. Copyright © 2005 John Wiley & Sons, Ltd.     

Ultrafast Orbital‐Oriented Control of Magnetization in Half‐Metallic La0.7Sr0.3MnO3 Films

Manipulating spins by ultrafast pulse laser provides a new avenue to switch the magnetization for spintronic applications. While the spin–orbit coupling is known to play a pivotal role in the ultrafast laser‐induced demagnetization, the effect of the anisotropic spin–orbit coupling on the transient magnetization remains an open issue. This study uncovers the role of anisotropic spin–orbit coupling in the spin dynamics in a half‐metallic La_0.7Sr_0.3MnO₃ film by ultrafast pump–probe technique. The magnetic order is found to be transiently enhanced or attenuated within the initial sub‐picosecond when the probe light is tuned to be s‐ or p‐polarized, respectively. The subsequent slow demagnetization amplitude follows the fourfold symmetry of the ${\mathrm{d}}_{x^2?y^2}$ orbitals as a function of the polarization angles of the probe light. A model based on the Elliott–Yafet spin‐flip scatterings is proposed to reveal that the transient magnetization enhancement is related to the spin‐mixed states arising from the anisotropic spin–orbit coupling. The findings provide new insights into the spin dynamics in magnetic systems with anisotropic spin–orbit coupling as well as perspectives for the ultrafast control of information process in spintronic devices.